Composition of matter



Patented May 15, 1945 2,376,313 COMPOSI ION OF MATTER Orland M. Relff, Woodbury, N. J., nssignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application May 8, 1942,"

Serial No. 442,230 T 4 Claims.

This application, which is a continuation-inpart of our co-pending application, Serial No.

330,694, filed April 20, 1940 (now Patent No.

2,319,190, issued May 11, 1943), relates to the production of certain new chemical compounds or compositions which may be generally designated as the sulphides of the metal salts of alkylsubstituted aryl ether acids. Although this invention is broadly concerned with chemical compounds or compositions coming within the scope of the above designated general classification, it contemplates as a preferred group within such general classification those compounds or compositions which are soluble or miscible with mineral oil.

The present invention is based upon the discovery that the oil-miscible sulphides of the metal salts of alkyl-substituted aryl ether acids are of multifunctional activity when blended with viscous mineral oil fractions in that they efiect improvement of several unrelated and related properties of the oil. For example, compounds or compositions of this preferred oil-miscible group which come within the general field of invention contemplated herein are effective, when blended in a minor proportion with mineral oil fractions of the lubricant type, to depress the pour point, improve the viscosity index (V. I.) and inhibit oxidation of the oil. By inhibiting oxidation these oil-miscible sulphides act to retard the formation of sludge and acidic products of oxidation. They also have a peptizing action on such sludge as may eventually be formed. Thus, any one of these preferred oil-miscible compounds or compositions may, for example, be used in internal combustion engine lubricants to retard or prevent the sticking of piston rings or prevent the corrosion of bearings, particularly those formed of alloy metals normally susceptible to corrosion, etc., and at the same time it will act to depress the pour point and improve the viscosity index of the oil. Through a proper choice of metal constituent, for example, lead, copper, tin or zinc, the load carrying capacity or lubricity of the oil may also be improved. For use, however, in internal combustion engine lubricants, compounds or compositions of the pres ent invention which contain tin are specially prefund. I

It should be understood that the use of these preferred oil-miscible compounds or compositions is not confined to lubricating oils, but they may be employed in any mineral oil fractions where one or more of the improved properties recited above is desired. In this regard, it is to be understood that the present invention is not concerned with mineral oil compositions to which these preferred oil-soluble compounds have been added. Such oil compositions form the subject matter of our co-pending application Serial No. 330,694, filed April 20, 1940. i

In the aforesaid co-pending application, which is directed to mineral oil compositions having incorporated therein the compounds or compositions of the present invention, and which is a continuation-in-part of my application Serial No. 229,876, filed September 11, 1938 (now Patent No. 2,198,292), I have distinguished over the chemical compounds or compositions described in said patent. For purposes of clarity, the differences between the compounds or compositions of the aforesaid patent and the compounds or compositions of the present invention are again set forth. The compounds or compositions of the patent (No. 2,198,292) are alkyl-substituted aryl ether acid salts; whereas the compounds or compositions of the present invention are sulphides of alkyl-substituted aryl ether salts wherein at least two of the alkylated aryl ether acid salt groups are interconnected by at least one atom of sulphur. Thus, through the introduction of sulphur in the manner or manners to be hereinafter described, I obtain what may be broadly termed a sulphide of an alkyl-substituted aryl ether carboxylic acid salt in which the carboxyl hydrogen is substituted with its equivalent weight of metal.

This general class of sulphides of metal salts distinguishes over the corresponding class of metal salts disclosed in Patent No. 2,198,292, in that they have increased effectiveness in retard ing the deleterious effects of oxidation when used as improving agents for mineral oil. In the preferred multifunctional class of these compounds or compositions, I have found that the sulphides possess improved pour depressant and viscosity index improving properties as wellas improved anti-oxidant properties over the corresponding salts of the aforesaid patent. The improved antioxidant properties are particularly significant in retarding the development of acidity in certain types of oils and under certain conditions of use.

It is to be understood that while my invention contemplates oil-miscible compounds or compositions of the type above referred to as a preferred class or group within the general field of invention, the invention is not limited to such oilmiscible compounds or compositions, since this whole class of new materials is possessed of valuable properties irrespective of oil-miscibility. For example, these compounds or compositions may be used as such as oil-soluble resins for use in paints and varnishes or as intermediaries .in the production of resins, resin-like materials, rubber substitutes, etc. Certain of the compounds or compositions are possessed of valuable phar maceutical, insecticidal, or similar properties, such, for example, as those characterized by the presence of a particular metal ether ca'rboxylate -alkyl-substituted hydroxyaromatics synthesis.

The compounds or compositions contemplated by the present invention may be considered as sulphides of alkyl-substituted hydroxyaromatic compounds in which the hydroxyl hydrogen is replaced with an organic acid group which in turn has its carboxyl hydrogen substituted with its equivalent weight of metal. Compounds of this general character include the sulphides of (phenols) wherein the hydroxyl hydrogen is replaced with an aliphatic or aromatic metal carboxylate group. These compounds or compositions are all characterized by the presence of an aromatic nucleus in which at least one nuclear hydrogen has been substituted with a monoor poly-basic ether acid or an oxy-acid substituent having the hydrogen of at least one carboxyl group replaced with its equivalent weight of metal.

The preferred compounds or compositions contemplated by this invention are further characterized by the fact that at least one hydrogen on the characterizing aryl hydroxide nucleus is substituted with an aliphatic hydrocarbon radical or group characteristic of an aliphatic hydrocarbon of high molecular weight which may be termed a heavy alkyl group. For obtaining the preferred group of compound or"compositions which possess the multifunctional oil-improving properties in addition to being miscible with mineral oil, I have found that this "heavy alkyl substituent in the sulphides of the aryl-ether acid salts under discussion must be derived from a predominantly straight chain aliphatic hydrocarbon of at least carbon atoms such as characterize petroleum wax. As a matter of fact, parafiln wax is considered to be a preferred source of the "heavy alkyl substituent, and it is for that reason that the preferred compounds or compositions described herein are referred to as waxsubstituted. It is to be understood, however, that the term wax" as used herein, is applied in a 'broad sense and is intended to include any pure compound or mixture of compounds predominantly aliphatic in nature and containing at least 20 carbon atoms which is susceptible of attachment to an aromatic nucleus to provide a substituent which, in the proper proportions, will impart to the characterizing group the multifunctional oil-improving properties referred to.

It will be understood that when a mixture of aliphatiedgdrocarbon compounds such as characterize petroleum wax, for example, is used to provide the heavy alkyl substituent, the resulting composition will be an intimate mixture of sulphides of alkyl-substituted aryl ether acid salts which differ from each other with respect to the nature of the heavy alkyl" substituent. In other words, where the alkylation of the aryl nucleus has been effected with a mixture of aliphatic hydrocarbons of at least 20 carbon atoms, the resulting composition will be a mixture of compounds differing in their heavy alkyl substituents but having in common the characterizing nuclear group hereinabove referred to.

The compounds or compositions of the present invention may be further considered as composed of at least two of the above described alkyl-sub-' stituted hydroxyaromatic compounds interconnected by at least one atom of sulphur and may MOOO-Z-O be characterized by the following general formulae:

,. MOOC-Z-O R v R O-Z-COOM BBB RBBR R R R. R 0-2-0001! (a) B R RRBRB BR 3BR in which n represents a whole number equal to at least 1 and preferably from 1 to 4. The group -0-Z-COOM represents what I may term an ether acid salt group wherein Z represents an aliphatic or aromatic radical and M represents the hydrogen equivalent of a metal. Thi group ('O'Z-COOM) may also be broadly defined as an ether carboxylic acid group in which the carboxyl hydrogen is substituted with its equivalent weight of metal. The symbol. R represents such groups as the following: hydrogen, alkyl, aralkyl, aryl, alkaryl, hydroxyl, ester (organic or inorganic acyl groups), keto, alkoxy, alkyl sulphide, aryl sulphide, aroxy, ether alcohol, aldehyde, thioaldehyde, oxime, amido, (organic or inorganic acyl groups), thioamido, carbamido, halogen, nitroso, amino, nitrosoamino, amidino, imino, N-thio, diazo, hydrazine, cyano, azoxy, azo and hydrazo; at least one R group being an oil-solubilizing alkyl group. In my preferred group of compounds or compositions, at least one R represents an oilsolubilizing aliphatic radical or group containing at least 20 carbon atoms, and which is, as indicated above, to be hereinafter described as a wax group. In my preferred group of compounds or compositions wherein at least one R is a wax group, the remaining Rs represent residual hydrogen which may be replaced, entirely or in part, with any of the groups of which R is broadly representative, and which may have a positive or negative or neutral oil-solubilizing effect.

For purposes of definition and description herein the group -O-Z-COOH, from which the abovedescribed -O-Z-COOM group is derived, shall be designated as the ether carboxylic acid group and the term aryl ether carboxylic acid salt is, as indicated above, inclusive of compounds wherein the group typified by-Z in the general formulae is either aryl or alkyl.

As aforesaid, Z may be an aromatic nucleus and,

employed as the metal M in compounds or condensation products of the aforesaid type to provide valuable oil addition -agents; The metals contemplated herein may be broadly classified as metals of groups I to VIII inclusive of the periodic system. These metals comprise the following: the alkali metals--lithium, sodium, potassium, rubidium and caesium; the alkaline earth groupberyllium, magnesium, calcium, strontium and barium; the metals zinc, cadmium, mercury, scandium; the metals aluminium, gallium, indium, thallium, titanium, zirconium, cerium, thorium, germanium, tin and lead; vanadium, columbium, and tantalum; arsenic, antimony and bismuth; chromium, molybdenum, tungsten and uranium; rhenium, manganese, iron, cobalt, and nickel, ruthenium, rhodium and palladium; osmium, iridium and platinum.

Some of the rare earth metals are given in the foregoing. Other rare earth metals suitable for use in the metal carboxylate group of these aryl ether sulphide condensation products are those now commercially available as the cerium and yttrium group, namely: a mixture of praseodymium, neodymium, samarium, europium, gadolinium,. terbium, dysprosium, holmium, erbium, thallium and lutecium.

The selection of metal will, of course, depend to a certain extent upon the use contemplated for the product; for example, when the compound or product is contemplated as a mineral oil additive the selection of the metal may be governed-by the character of the oil in which the addition agent is to be added and the conditions under which it is to be used. Certain metals, such as lead, zinc and tin, for example, may contribute to the oiliness characteristics of the oil. As pointed out hereinabove, my present work indicates tin as being a specially preferred metal for use in addition agents for internal combustion engine lubricants.

As aforesaid, it is important that the heavy alkyl substituent in the sulphide of the aryl ether carboxylic acid salts, preferred for use as oil addition agents, contain a heavy alkyl substituent in suillcient amount to render the compound or composition oil-miscible. The heavy alkyl substituent must comprise a sufficient proportion of the composition as a whole so that when blended with a mineral oil it will remain in solution or colloidal suspension under normal conditions of handling and use. It appears that there is a critical range in the degree of wax-substitution of, the aryl nucleus characterizing the aryl hydroxide used as a starting material below which the product will notsatisfy the requirements for oil-miscibility. The critical range in the degree of wax-substitution of the aryl nucleus in these preferred sulphides of wax-aryl ether acid salts may vary with:

a. The mineral oil fraction in which the improv ing agent is to be used,

b. The character of the aryl nucleus (monocyclic or polycyclic and monohydric or polyhydric),

c. Monoor polysubstitution of the aryl nucleus,

and

d. Other substituents on the aryl nucleus which may be of positive or negative or of neutral solubilizing activity.

For example, a polycyclic nucleus appears to require a higher degree of wax-substitution than a monocyclic nucleus and a polyhydric compound requires a higher degree of wax-substitution than a monohydric compound.

In view of the foregoing variables, it would be impracticable and probably misleading to attempt to give an expression and figure which would indicate accurately the proper ratio of aryl hydroxide constituent to the wax-substituted aryl hydroxide constituent which would express a degree of wax-substitution satisfying all cases taking these variables into account.- In general, however, it may be said that in these preferred coinpounds having the multifunctional oil improving properties, the ratio by weight of the aryl hydroxide component in the wax-substituted product (from which the sulphide of the wax-aryl ether acid salt is obtained) to the corresponding wax-substituted aryl hydroxide should not be greater than about 20 parts by weight of the into account other possible substituents in'thecharacterizing nucleus than the heavy alkyl or wax and hydroxyl groups, but since the wax substituent is primarily relied upon in the preferred compounds or compositions contemplated herein as oil-improving agents, it is believed that the foregoing ratio and limit will serve as a working guide for the preparation of these preferred materials. It is to be understood, however, that the present invention is not limited to.com1pounds of the type preferred for use as mineral oil addition agents but includes the general class of compounds. described herein, irrespective of use or purpose for which they are prepared. I

As indicated above by. the general formulae. the term sulphide as used herein is inclusive of the monosulphides, disulphides, trisulphides, tetrasulphides, etc., that is, it includes both monosulphides and polysulphides, and it is also intended to include such polymers and related derivatives as may be formed by the hereinafter described procedures employed to illustrate the synthesis of the compounds or compositions contemplated herein.

Several procedures may be resorted to in synthesizing the sulphides of alkylated aryl ether acid salts contemplated herein. One general procedure is to react the corresponding alkylated aryl ether acid, the preparation of which is described in Patent No. 2,198,292, with a sulphur halide followed by substitution of the carboxyl hydrogen with the desired metal. Another procedure of this type involves condensation of the alkali metal carboxylate of the alkylated aryl ether acid with a sulphur halide, whereby a sulphide of lighter color may be obtained. The sulphides of the alkali metal carboxylates thus formed may be then converted by metathesis to the, salt of another metal when desirable.

In the event sulphur dichloride (S012) is used in the general procedures described above, the condensation product will be in the nature of a monosulphide (or polymer thereof); sulphur monochlorlde will yield the corresponding disulphide (or polymer thereof) and, of course, a mixture of sulphur halides may be employed to obtain a'mixture of sulphides. Elementary sulphur may be employed as the condensation reagent, but this is not considered the most desirable procedure.

Sulphur derivatives of higher sulphur content may be obtained by reacting a condensation prodnot having the disulphide linkage with alkali polysulphides or with an alkyl tetrasulphide. Such higher sulphur derivatives may also be obtained by first reducing the disulphide to form a thiophenol .or aryl mercaptan of the alkylated aryl ether acid and then reacting the mercaptan with sulphur dichloride (to form the trisulphide) or with sulphur monochloride (to form the tetrasulphide).

The alkylated aryl ether acids and their alkali metal salts, used in preparing the sulphides may be obtained in various ways. The details in desirable procedures for preparing the alkali metal salts and alkylated aryl ether acids are described in Patent No. 2,198,292.

For example, in preparing the alkyl substituted aryl ether acid salts, an aryl hydroxide is first alkylated to substitute the aryl nucleus with alkyl groups to the desired extent. The hydroxyl hydrogen is t en substituted with an alkali metal to form the ali kylated aryl alkali metal hydroxylate, which may then be reacted with the alkali metal salt of a halogenated organic carboxylic acid to form the ether acid salt. The alkylated aryl alkali metal hydroxylate may then be reacted with the corresponding alkali metal salt of a halo-fatty acid to obtain the alkali metal salt of the alkylated aroxy-aliphatic carboxylic acid.

In the event the alkylated aryl ether acid is obtained as the acid, the corresponding sulphides can be obtained by dissolving the alkylated aryl ether acid in a suitable solvent such as carbon disulphide, benzene, chlorbenzene, ethylene dichloride, Stoddard solvent. or the like. The temperature of the solution may be brought up to about 100 F. and the sul hur halide or mixture of sulphur halides added in the ratio of from about /2 to 1 mol of sulphur halide per mol of the alkylated aryl ether acid. The addition of the sulphur halide should be sufficiently slow to prevent the temperature substantially exceeding 100 F., and the mixture may be held at that temperature for about 1 hour to complete formation of the sulphur derivative. Hydrogen chloride is evolved in the reaction resulting in fixation of the sulphur in the aryl nucleus. As regards the temperature of the reaction it is to be understood that the reaction can be carried out at various temperatures from room temperature up to the boiling point of the solvent, but it is preferable for obtaining light colored products that the temperature is not too high. The mixture is waterwashed to remove dissolved hydrochloric acid and the free aryl ether acid is converted to its corresponding alkali salt by reaction with an alkali alcoholate. Salts of other metals are obtained by metathesis of the alkali salt with a normal inorganic or fatty acid salt or oxy salt of the desired metal, carrying out the reaction in aqueous or non-aqueous medium.

When the alkylated aryl ether acid starting material for sulphur condensation is obtained as the alkali carboxylate or alkali metal salt, the corresponding sulphide derivatives can be obtained by reacting with sulphur halide without first liberating the free acid and in this case free HCl is not evolved unless an amount of sulphur halide in excess of the sodium content is used. the HCl being converted to sodium chloride by reaction with the carboxylate alkali. When the alkali salt is used as an initial reactant the procedure is, in general, the same as that described above except that solvents such as carbon disulphide and ethylene dichloride should be replaced with solvents such as alcohol, benzene, or chlorbenzene to avoid side reactions with the alkali derivative.

When alkylated phenols (such as wax-phenols) or the alkali salts thereof (such as wax sodium phenate) are directly sulphurized before converting to the ether acid derivative, the sulphu rization is carried out as outlined above, avoiding reactive solvents such as carbon disulphide and ethylene dichloride when the alkali salts are used.

Metal carboxylates of alkylated aryl ether acid sulphides can be made from the alkylated aryl ether acid sulphides obtained according to the foregoing procedures by reacting the anhydrous acid with the alcoholate of the desired metal; or by converting the free acid to an alkali salt and reacting the same with a soluble salt of the desired metal to form polyvalentmetal salts by double decomposition.

Examples of alkali metal salts of halo-aliphatic acids (as chlor-aliphatic acids) which may be used in the foregoing typical procedure are: sodium chloracetate, propionate, butyrate, octylate, caprylate, palmitate, stearate, etc.; and corresponding compounds of polybasic acids as: sodium chlorsuccinate, adipate, etc. It is preferred that the reactions be carried out in the presence of a non-aqueous medium.

Another desirable procedure consists in reacting an ester of the chlor-fatty acid instead of the alkali salt with the alkylated aryl metal hydroxylate, saponifying the ester group to form the salt, and subsequently sulphurizing as hereinabove described.

As indicated above, Z may represent either an aliphatic or aromatic radical. Alkali salts of diaryl ether acids, wherein the group -Z-COOM in the ether acid substituent -O-Z-COOM) represents the residue of an aromatic acid salt, can be synthesized by reacting an alkyl-substituted aryl alkali metal hydroxylate with a brom-aryl alkali metal carboxylate such as .brom-sodium benzoate (Br-CeH4-COQNa) in the presence of a small percentage of powdered copper as a catalyst. In such case, Z is -CsH4-. Other aromatic acids whose derivatives may be used are phthalic, naphthoic, cinnamic, etc.

The aryl hydroxide used as the initial reactant in the alkylation step may be monoor polycyclic and monoor poly-hydric. Examples of these compounds are phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxyldiphenyl, benzyl-phenol, phenyl-ethyl-phenokphenol resins, meta-hydroxydiphenyl, guaiacol, alpha and beta naphthol, alpha and beta methyl naphthol, tolyl naphthol, xylyl naphthol, benzyl naphthol, anthranol, phenyl methyl napthol, phenanthrol, anisole. beta naphthyl methyl ether, chlorphenoi, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, particular preference being given to phenol and alpha and beta naphthol.

The alkylation of the aryl hydroxide with heavy alkyl groups may be accomplished in various ways, such as by a Friedel-Crafts reaction, using a halogenated aliphatic hydrocarbon compound preferably a high molecular weight aliphatic compound or a mixture thereof such as chlorinated petroleum wax, or by reaction with unsaturated high molecular weight aliphatic alcohols or higher alcohols in the presence of HzSOq. as a catalyst. High molecular weight unsaturated aliphatic hydrocarbons useful in this regard are eicosylene, cerotene, melene, etc., and alcohols useful for this purpose are ceryl alcohol, myricyl alcohol, etc. In general it is preferred toconvert the alcohol to the corresponding halide (or p'olyhalide) and then condense the same with the hydroxyaromatic compound by the Friedel-Craftsl reaction.

When it is desired to obtain a compound or composition in which the characterizing aryl nucleus contains, in additionto, or instead of, residual hydrogen, another substituent or other substituents of the type classified above in the foregoing general formulae asR, it is desirable to introduce such substituent groups except aralkyl. aryl, alkaryl, halogen, hydroxyl and aroxy, after alkylation, and generally before introduction of the ether acid group. The usual methods for introduction of these substituents into non-alkylated hydroxyaromatic compounds may be employed in connection with the alkylated or wax-substituted hydroxyaromatic compounds. To those skilled in the art, it will be apparent that the R substituents are mainly derivatives of phenolic (OH) groups, amino groups, aldehyde and keto groups, and carboxyl groups. Methods for the introduction ofsuch base substituents along with -Z-COOM groups will be apparent from methods described in the aforesaid Patent No. 2,198,292 and Patent No. 2,197,835. H

The following description illustrates preferred procedures which may be followed in synthesizing the sulphides of the metal salts of wax aryl ether acids contemplated by this invention. The compounds or compositions obtained from the syntheses described below fall into that class or group of products hereinabove referred to as preferred because of their oil-solubility or their multifunctional activity when blended with mineral oil fractions. As will be apparent to those skilled in the art, compounds or compositions having a combined phenol content in excess of that necessary for oil-miscibility may be readily obtained by using a chlorinated alkyl (as wax) having a chlorine content substantially higher than given below or by changing the ratio of the reactants (chlorwax and phenolic compound).

PREPARATION or SULPHIDES F WAX-SUBSTITUTED PHENOXY-ARYL Ernnx Acm SALTS 1. Alkylation of phenol A paramn wax melting at approximately 126 F. and predominantly comprised of compounds having at least 20 carbon atoms in their molecules is melted and heated to about 200 F. after which chlorine is bubbled therethrough until the wax has absorbed from 16% to 20% of chlorine, such product having an average composition between a monochlor wax and a dichlor wax or corresponding roughly to a dichlor wax. Preferably the chlorination is continued until about by weight of the "chlorwax formed is chlorine. A quantity of chlorwax thus obtained, containing 3 atomic proportions of chlorine, is heated to a temperature varying from just above its melting point to not over 150 F. and 1 mol of phenol (CsI-I5OH) is admixed therewith. The mixture is heated to about 150 F. and .a quantity of anhydrous aluminum chloride corresponding to say about 3% of the weight of chlorwax is slowly added to the mixture with active stirring. The rate of addition of the AlCla should be sufficiently slow to avoid violent foaming, and during such addition the temperature should be held at about 150 F. After the'AlCla has been added, the temperature of the mixture may be increased slowly over a period of from to 25 minutes to a temperature in the neighborhood of about 250' 1". and then should be more slowly increased to from about 300 F. to about 350 F. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture m'ay be held at 350 F. for a short time to allow completion of the reaction. But, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extended length of time.

It is important that all unreacted or non-alkylated hydroxyaromatic material (phenol) remaining after the alkylation reaction be removed. Such removal can be effected generally by water-washing, but it is preferable to treat the water-washed product with super-heated steam, thereby insuring complete removal of the unreacted phenolic material and accomplishing the drying of the product in the same operation.

A wax-substituted phenol prepared according to the above procedure, in which a quantity of chlorwax containing 3 atomic proportions of chlorine (20% chlorine in the chlorwax) is reacted with 1 mol of phenol, may, for brevity herein, be designated as wax-phenol (3-20). Parenthetical expressions of .this type (A-B) will be used hereinafter in connection. with the alkylated hydroxyaromatic compounds to designate (A) the number of atomic proportions of chlorine in chloraliphatic material reacted with 1 mol of hydroxyaromatic compound in the Friedel-Crafts reaction, and '(B) the chlorine content of the chloraliphatic material. above example A=3 and 13:20.

In the 2. Formation of war-substituted alkali metal phenate As an example of this step in the preparation of our oilimproving agents, wax-substituted sodium phenate can be prepared by the reaction of wax-phenol with metallic sodium in th presence of a non-oxidizing gas. The reaction mixture is heated at 500 F. during a 2-hour period with rapid stirring to produce finely divided sodium and thereby accelerate the reaction The proportions of reactants which were used in preparing a wax-substituted alkali metal phenate according to the above procedure were:

Grams Wax-phenol (13.2% combined phenol content) -.a 500 Sodium or equivalent amount of potassium 16 Wax alkali metal phenates may also be prepared by reaction of a wax phenol with an alcoholate of th alkali metal.

3. Formation of sulphides of ether acid salts from wax-alkali metal phenate a. A solution of 27.5 grams of monochloracetic acid in c. c. of anhydrous ethanol was converted to sodium chloracetate by adding thereto a standard alcohol solution of sodium hydroxide, maintaining the temperature of the reaction mixture at about 100 F. This sodium chloracetate mixture was then added to a solution of 200 grams of wax sodium phenate (3-20) in 600 grams of Stoddard's solvent, and the mixture was stirred at F. during a 2-hour period to form the wax-substituted phenoxy sodium acetate. The mixture was then sulphurized by lowering the temperature to about 100 F. and adding with rapid stirring 19.7 grams of sulphur monochloride at a rate suillciently slow to avoid appreciable rise a in the temperature of the mixture by heat of reaction developed. The mixture was then stirred at this temperature about 1 hour to complete the sulphurization, followed by distilling the alcohol and water-washing or dry filtering the mixture to obtain the wax phenoxy acetic acid disulphide, which was approximately a A. blend in Stoddards solvent.

, A solution of 100 grams of wax-phenoxy acetic acid disulphide in about 300 grams Stoddards solvent as formed by the above procedure, was mixed with 3.35 grams of sodium in solution in butanol as sodium butylate, followed by heating the mixture at about 200 F. for 1 hour to form the sodium salt of the wax phenoxy acetic acid disulphide. An alcohol solution of 13.8 grams of anhydrous stannous chloride was then added and the mixture was heated at about 200 F. for 1 hour, followed by distillation of the butanol to obtain the stannous salt. The reaction mixture wa then filtered through Hi-Flo to purify the product. which was approximately a blend of the stannous salt of wax phenoxy acetic acid disulphide in Stoddards olvent. By distilling off the Stoddards solvent, the pure product is obtained.

The wax-phenoxy acetic acid used in certain of the hereinafter describedprocedures can be obtained by neutralizing the reaction mixture, before purification, with HCl. The free acid is purified by water-washing the product to remove reaction salts and drying to give a concentrated solvent blend of the finished product.

b. By use of the above procedure, the cobaltous salt of wax-phenoxy acetic acid disulphide was formed by substituting an equivalent amount of cobaltous chloride for stannous chloride.

0. A solution of 100 grams of wax sodium phenate in 300 grams of kerosene (or other suitable solvent) was mixed with 29 grams of brom sodium benzoate (Br-C6H4-COONa) and stirred at a reaction temperature of about 400 F. during a 4-hour period in the presence of-copper powder as catalyst to form the sodium salt of waxphenoxy benzoic acid. The free acid was ob tained by treating the reaction product with aqueous hydrochloric acid, followed by water-washing and drying the mixture to obtain the purified product. The free acid was then diluted with one volume of chlorbenzene and converted to the sodium salt by adding an equivalent of sodium butylate and heating at about 200 F. for 1 hour before sulphurizing the mixture. The sulphurization was carried out by adding 9.8 grams of sulphur monochloride at about 100 F. at a rate sufficiently slow to avoid appreciable temperature rise by the heat of reaction developed, followed by stirring the mixture 1 hour at this temperature to complete the sulphurization. The product was purified by water-washing the mixture until the aqueous extract was neutral, followed by distillation of the chlorbenzene diluent to obtain the wax-phenoxy benzoic acid disulphide which was approximately a A blend in kerosene.

The stannous salt of the wax-phenoxy-benzoic acid disulphide was prepared by adding 0.85 gram of sodium in solution in butanol as sodium butylate, to 100 grams of the kerosene blend of the free acid prepared as described above, followed by adding an alcohol solution of 3.47 grams of anhydrous stannous chloride. The mixture was then heated to the reflux temperature (about 225 F.) for 1 hour, followed by distillation of the alcohol to obtain the stannous salt concentrate in mineral .oil. The mixture was then filtered through Hi- F10" and steam treated at 300 F. until all traces of alcohol were removed to obtain the finished product in kerosene, and the pure product per se may be obtained by distilling off the kerosene.

Sulphides of wax-substituted aryl ether acid salts, which represent a preferred group of compounds or compositions, of the general character described above which are derived from wax phenol may be broadly classified as sulphides of wax phenyl ether acid salts. Corresponding sulphides can be prepared from wax-substituted hydroxyaromatic compounds other than phenol (CsHsOH) ,-either monoor polycyclic and substituted or unsubstituted, such, for example, as'wax naphthol (3-14) having a combined naphthol content of 16% and equivalent phenol content or phenolic ratio of 10.4%. As aforesaid, other high molecular weight aliphatic compounds or materials than petroleum wax may be used as the source for the heavy alkyl (wax) substituent, and it is also emphasized that the invention is not limited to products obtained from acetic acid or benzoic acid as a source for the ether acid substituent but any halogenated aliphatic or aromatic acid, including the alkali salt thereof, may be used to obtain various aliphatic and aromatic radicals or groups in the ether acid salt or oxyacid salt substituent. I

Sulphides of wax-aryl ether acid salts of the type described above are highlyviscous rubberlike products, which with the phenolic ratio properly controlled are readily soluble in'mineral oils. Their color is such that they can be readily blended with light colored mineral oil fractions without substantial darkening of the oil, which makes them particularly desirable for use in this connection.

Although products of the oil-miscible type are designated herein as preferred, because of their multifunctional improving properties in mineral oil blends, it is again emphasized that the invention is not limited to sulphides of metal salts of wax-aryl ether acids in which the phenolic ratio is adjusted for oil solubility, but that it is inclusive of this entire field of products irrespective of oil-solubility.

Listed below are a number of typical compounds of the type contemplated herein. The procedures for preparing these compounds or reaction products will be apparent to those skilled in the art from the foregoing examples of representative procedures.

Stannous carboxylate of wax phenoxy acetic acid disulphide Barium carboxylate of diamyl phenoxy propionic acid monosulpihde Calcium carboxylate of dodecyl naphthoxy caprylic acid tetrasulphide Sodiumcarboxylate of wax phenoxy stearic acid disulphide cobaltous carboxylate of wax'phenoxy acetic acid disulphide stannous carboxylate of wax phenoxy benzoic acid disulphide It is to be understood that the foregoing examples of procedures and typical products or compounds are merely illustrativeland that the invention includes within its scope such changes and modifications as fairly come within the spirit of the appended claims. For example, although the foregoing description is confined to sulphides and polysulphides, the invention contemplates selenides and tellurides insofar as the corresponding selenium and tellurium derivatives are 2. As a new composition of matter, stannous salt of paraflin wax-substituted phenoxy acetic acid disulflde.

3. As a new composition of matter, cobaltous salt of paramn wax-substituted acid disulflde.

4. Asa. new composition of matter, stannous salt of paraflln wax-substituted phenoxy benzoic acid disulfide.

ORLAND M. REIFF.

phenoxy acetic i 

